86791-38-0Relevant articles and documents
Lewis Acid Catalyzed Enantioselective Photochemical Rearrangements on the Singlet Potential Energy Surface
Leverenz, Malte,Merten, Christian,Dreuw, Andreas,Bach, Thorsten
supporting information, p. 20053 - 20057 (2019/12/30)
The oxadi-methane rearrangement of 2,4-cyclohexadienones to bicyclic ketones was found to proceed with high enantioselectivity (92-97% ee) in the presence of catalytic amounts of a chiral Lewis acid (15 examples, 52-80% yield). A notable feature of the transformation is the fact that it proceeds on the singlet hypersurface and that no triplet intermediates are involved. Rapid racemic background reactions were therefore avoided, and the catalyst loading could be kept low (10 mol %). Computational studies suggest that the enantioselectivity is determined within a Lewis acid bound singlet intermediate via a conical intersection. The utility of the method was demonstrated by a concise synthesis of the natural product trans-chrysanthemic acid.
HIGH YIELD SYNTHESIS OF FILICINIC ACID, BASED ON THE POLYCHLORINATION OF 4,4-DIMETHYL-2-CYCLOHEXENONE PART II : CONVERSION OF 2,3,5,6-TETRACHLORO-4,4-DIMETHYL-2,5-CYCLOHEXADIENONE INTO FILICINIC ACID AND RELATED CYCLOHEXADIENONES
Buyck, L. De,Kimpe, N. De,Verhe, R.,Schamp, N.
, p. 241 - 248 (2007/10/02)
Filicinic acid (5) was prepared in 75-80percent overall yield from 4,4-dimethyl-2-cyclohexenone (1).The key intermediate, tetrachlorodienone 2, underwent facile substitution of both β-chlorine substituents by methoxide affording the bis enol ether 3 which was converted into dichlorofilicinic acid 4 in hot 85percent sulfuric acid.Monohydroxy derivatives were obtained by treatment of 2 or 3 with hydroxide.Palladium-catalysed low-pressure hydrogenation of 4 under appropiate conditions produced monochlorofilicinic acid, filicinic acid or 5-hydroxy-4,4-dimethyl-1,3-cyclohexanedione (8) with high selectivity.